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Fabrication of hierarchically porous silica nanospheres through sol–gel process and pseudomorphic transformation

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Abstract

Hierarchically porous silica nanospheres with well-defined morphology and uniform particle size had been synthesized through a multistep sol–gel method combined with pseudomorphic transformation in the presence of polyvinylpyrrolidone (PVP) and cetyltrimethylammoium bromide (CTAB) as dual template. The prepared materials were characterized by small-angle X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and nitrogen physical adsorption techniques. The preparation process and the origin of hierarchical structure were also investigated. It had been shown that the hierarchical structure of synthesized materials comprises wormlike framework mesopores with diameters of about 3 nm and bubble-like pores with diameters of 20–30 nm. CTAB and PVP behave as dual-template and are responsible for the formation of the mesopores and big pores, respectively. Not only the porous structure, but also the morphology and particle size of hierarchical materials can be adjusted by controlling the addition of PVP. In addition, the formation process of hierarchically porous silica was investigated by transmission electron microscopy, FT-IR spectra and thermo-gravimetric curves and a possible synthetic mechanism had been proposed.

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References

  1. Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS (1992) Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature 359:710–712

    Article  Google Scholar 

  2. Zhao DY, Feng JL, Huo QS, Melosh N, Fredrickson GH, Chmelka BF, Stucky GD (1998) Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science 279:548–552

    Article  Google Scholar 

  3. Kim SS, Zhang WZ, Pinnavaia TJ (1998) Ultrastable mesostructured silica vesicles. Science 282:1302–1305

    Article  Google Scholar 

  4. Zhang WZ, Fröba M, Wang JL, Tanev PT, Wong J, Pinnavaia TJ (1996) Mesoporous titanosilicate molecular sieves prepared at ambient temperature by electrostatic (S+I−, S+X−I+) and neutral (SoIo) assembly pathways: a comparison of physical properties and catalytic activity for peroxide oxidations. J Am Chem Soc 118:9164–9171

    Article  Google Scholar 

  5. Du X, He JH (2012) Amino-functionalized silica nanoparticles with center-radially hierarchical mesopores as ideal catalyst carriers. Nanoscale 4:852–859

    Article  Google Scholar 

  6. Zhu YF, Shi JL, Chen HR, Shen WH, Dong XP (2005) A facile method to synthesize novel hollow mesoporous silica spheres and advanced storage property. Micropor Mesopor Mater 84:218–222

    Article  Google Scholar 

  7. Sun ZK, Deng YH, Wei J, Gu D, Tu B, Zhao DY (2011) Hierarchically ordered macro-/mesoporous silica monolith: tuning macropore entrance size for size-selective adsorption of proteins. Chem Mater 23:2176–2184

    Article  Google Scholar 

  8. Sel O, Sallard S, Brezesinski T, Rathouský J, Dunphy DR, Collord A, Smarsly BM (2007) Periodically ordered meso- and macroporous SiO2 thin films and their induced electrochemical activity as a function of pore hierarchy. Adv Funct Mater 17:3241–3250

    Article  Google Scholar 

  9. Zhu YF, Shi JL, Shen WH, Dong XP, Feng JW, Ruan ML, Li YS (2005) Stimuli-responsive controlled drug release from a hollow mesoporous silica sphere/polyelectrolyte multilayer core-shell structure. Angew Chem Int Ed 44:5083–5087

    Article  Google Scholar 

  10. Chen HM, He JH, Tang HM, Yan CX (2008) Porous silica nanocapsules and nanospheres: dynamic self-assembly synthesis and application in controlled release. Chem Mater 20:5894–5900

    Article  Google Scholar 

  11. Yang PD, Deng T, Zhao DY, Feng PY, Pine D, Chmelka BF, Whitesides GM, Stucky GD (1998) Hierarchically ordered oxides. Science 282:2244–2246

    Article  Google Scholar 

  12. Blas H, Save M, Pasetto P, Boissière C, Sanchez C, Charleux B (2008) Elaboration of monodisperse spherical hollow particles with ordered mesoporous silica shells via dual latex/surfactant templating: radial orientation of mesopore channels. Langmuir 24:13132–13137

    Article  Google Scholar 

  13. Wang JG, Xiao Q, Zhou HJ, Sun PC, Yuan ZY, Li BH, Ding DT, Shi AC, Chen TH (2006) Budded, mesoporous silica hollow spheres: hierarchical structure controlled by kinetic self-assembly. Adv Mater 18:3824–3828

    Google Scholar 

  14. Zhang HF, Hardy GC, Rosseinsky MJ, Cooper AI (2003) Uniform emulsion-templated silica beads with high pore volume and hierarchical porosity. Adv Mater 15:78–81

    Article  Google Scholar 

  15. Chen YL, Li Y, Chen YX, Liu XJ, Zhang M, Li BZ, Yang YG (2009) Preparation of hollow silica spheres with holes on the shells. Chem Commun 5177–5179

  16. Zhao WR, Lang MD, Li YS, Li L, Shi JL (2009) Fabrication of uniform hollow mesoporous silica spheres and ellipsoids of tunable size through a facile hard-templating route. J Mater Chem 19:2778–2783

    Article  Google Scholar 

  17. Yu MH, Wang HN, Zhou XF, Yuan P, Yu CZ (2007) One template synthesis of raspberry-like hierarchical siliceous hollow spheres. J Am Chem Soc 129:14576–14577

    Article  Google Scholar 

  18. Yeh YQ, Chen BC, Lin HP, Tang CY (2006) Synthesis of hollow silica spheres with mesostructured shell using cationic-anionic-neutral block copolymer ternary surfactants. Langmuir 22:6–9

    Article  Google Scholar 

  19. Wang JG, Zhou HJ, Sun PC, Ding DT, Chen TH (2010) Hollow carved single-crystal mesoporous silica templated by mesomorphous polyelectrolyte-surfactant complexes. Chem Mater 22:3829–3831

    Article  Google Scholar 

  20. Su Y, Yan R, Dan MH, Xu JX, Wang D, Zhang WQ, Liu SX (2011) Synthesis of hierarchical hollow silica microspheres containing surface nanoparticles employing the quasi-hard template of poly(4-vinylpyridine) microspheres. Langmuir 27:8983–8989

    Article  Google Scholar 

  21. Qi GG, Wang YB, Estevez L, Switzer AK, Duan XN, Yang XF, Giannelis EP (2010) Facile and scalable synthesis of monodispersed spherical capsules with a mesoporous shell. Chem Mater 22:2693–2695

    Article  Google Scholar 

  22. Bau L, Bartova B, Arduini M, Mancin F (2009) Surfactant-free synthesis of mesoporous and hollow silica nanoparticles with an inorganic template. Chem Commun 7584–7586

  23. Tan B, Rankin SE (2005) Dual latex/surfactant templating of hollow spherical silica particles with ordered mesoporous shells. Langmuir 21:8180–8187

    Article  Google Scholar 

  24. Zhang AF, Zhang YC, Xing N, Hou KK, Guo XW (2009) Hollow silica spheres with a novel mesoporous shell perforated vertically by hexagonally arrayed cylindrical nanochannels. Chem Mater 21:4122–4126

    Article  Google Scholar 

  25. Du L, Song HY, Liao SJ (2009) Tuning the morphology of mesoporous silica by using various template combinations. Appl Surf Sci 255:9365–9370

    Article  Google Scholar 

  26. Park SJ, Kim YJ, Park SJ (2008) Size-dependent shape evolution of silica nanoparticles into hollow structures. Langmuir 24:12134–12137

    Article  Google Scholar 

  27. Zhang Q, Zhang TR, Ge JP, Yin YD (2008) Permeable silica shell through surface-protected etching. Nano Lett 8:2867–2871

    Article  Google Scholar 

  28. Yu QY, Wang PP, Hu S, Hui JF, Zhuang J, Wang X (2011) Hydrothermal synthesis of hollow silica spheres under acidic conditions. Langmuir 27:7185–7191

    Article  Google Scholar 

  29. Zhang TR, Ge JP, Hu YX, Zhang Q, Aloni S, Yin YD (2008) Formation of hollow silica colloids through a spontaneous dissolution-regrowth process. Angew Chem Int Ed 47:5806–5811

    Article  Google Scholar 

  30. Wong YJ, Zhu LF, Teo WS, Tan YW, Yang YH, Wang C, Chen HY (2011) Revisiting the Stöber method: in homogeneity in silica shells. J Am Chem Soc 133:11422–11425

    Article  Google Scholar 

  31. Hu YX, Zhang Q, Goebl J, Zhang TR, Yin YD (2010) Control over the permeation of silica nanoshells by surface-protected etching with water. Phys Chem Chem Phys 12:11836–11842

    Article  Google Scholar 

  32. Du X, He JH (2010) Fine-tuning of silica nanosphere structure by simple regulation of the volume ratio of cosolvents. Langmuir 26:10057–10062

    Article  Google Scholar 

  33. Wiley B, Sun YG, Mayers B, Xia YN (2005) Shape-controlled synthesis of metal nanostructures: the case of silver. Chem Eur J 11:454–463

    Article  Google Scholar 

  34. Yin J, Wang J, Zhang YJ, Li HQ, Song YJ, Jin CZ, Lu T, Zhang T (2011) Monomorphic platinum octapod and tripod nanocrystals synthesized by an iron nitrate modified polyol process. Chem Commun 47:11966–11968

    Article  Google Scholar 

  35. Fujita N, Asai M, Yamashita T, Shinkai S (2004) Sol-gel transcription of silica-based hybrid nanostructures using poly(N-vinylpyrrolidone)-coated [60] fullerene, single-walled carbon nanotube and block copolymer templates. J Mater Chem 14:2106–2114

    Article  Google Scholar 

  36. Büchel G, Unger KK, Matsumoto A, Tsutsumi K (1998) A novel pathway for synthesis of submicrometer-size solid core/mesoporous shell silica spheres. Adv Mater 10:1036–1038

    Article  Google Scholar 

  37. Galarneau A, Iapichella J, Bonhomme K, Renzo FD, Kooyman P, Terasaki O, Fajula F (2006) Controlling the morphology of mesostructured silicas by pseudomorphic transformation: a route towards applications. Adv Funct Mater 16:1657–1667

    Article  Google Scholar 

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Acknowledgments

The financial support obtained from the Chinese Academy of Sciences for “100 Talents” Project, the National Natural Science Foundation of China (No. 11079036, 21003124) and the Natural Science Foundation of Liaoning Province (No. 20092173) is greatly acknowledged.

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Authors and Affiliations

  1. Laboratory of Catalysts and New Materials for Aerospace, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023, China

    Changzi Jin, Junhu Wang, Yanjie Wang, Hailian Tang & Ting Lu

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  1. Changzi Jin
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  2. Junhu Wang
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  3. Yanjie Wang
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  4. Hailian Tang
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  5. Ting Lu
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Correspondence to Junhu Wang.

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Jin, C., Wang, J., Wang, Y. et al. Fabrication of hierarchically porous silica nanospheres through sol–gel process and pseudomorphic transformation. J Sol-Gel Sci Technol 70, 53–61 (2014). https://doi.org/10.1007/s10971-014-3273-0

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  • DOI: https://doi.org/10.1007/s10971-014-3273-0

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